Nitro anilino-polyalkylene polyamines and the salts thereof

ABSTRACT

Compounds of the formula and their salts   IN WHICH R1 and R2 each represents hydrogen or chloro, m represents an integer 2 or 3 and n represents an integer 1, 2, 3, or 4, R3 represents hydrogen or   WHEREIN R1 and R2 each is defined as above.

D United States Patent 3,622,608

[72] Inventors Gustav Schaier; 5 k h Cited v gggfg' UNITED STATESPATENTS [21] APPL 843,820 3,412,130 11/1968 Schafer et a1. 260/5705 X[22] Filed July 22, 1969 Primary Examiner-Robert V. Hines [45] Pa n 1971AnorneyCurtis, Morris and Safford [73] Assignee Farbwerke HoechstAktiengeselbchafl vormals Meister, Lucius & Brunlng Frankfurt/Main,German ABSTRACT: Compounds of the formula and their salts [32] PriorityOct. 28, 1965 [33] Germany [31] P475313 -N0,

Continuation-impart of application Ser. No. I 588,291, Oct. 21, 1966,now abandoned. NHl(CHi)mNH1,.( H),.NHR This application July 22,1969,Ser. No. R 843,820

in which R and R, each represents hydrogen or chloro, m represents aninteger 2 or 3 and n represents an integer l, 2, 3, [54] NITROANlLlNO-POLYALKYLENE POLYAMINES AND THE SALTS THEREOF or 4, R3represents hydrogen or 6 Claims, No Drawings R1 [52] US. Cl 260/4293,OIN

1 17/144, 260/5012, 260/5705 PA [51] Int. Cl C071 3/06 [50] Field ofSearch 260/5012,

' wherein R, and R each is defined as above.

NITRO ANlLINO-POLYALKYLENE POLYAMINES AND THE SALTS THEREOF Thisapplication is a continuation in part application of our copendingapplication Ser. No. 588,291 filed Oct. 21, 1966 and now abandoned.

The present invention provides new water-soluble basic dyestuffs andtheir salts and a process for preparing them; particularly, it concernsbasic dyestuffs of the formula l in which R, and R each representshydrogen or chlorine atoms, m represents an integer 2 or 3 and nrepresents an integer l, 2, 3 or 4, R represents a hydrogen atom or thegroup wherein R and R, each is defined as above, or the salt of aninorganic or organic acid thereof.

We have found that new water-soluble basic dyestuffs of the formula (1)as indicated and defined above can be prepared by reacting l mol of apolyamine of the formula (2) H,N(CH ),,,NH],,(CH,) ,,,-NH, (2) wherein mand n are defined as above, with at least 1 mol of a compound of theformula (3) in which X represents a chlorine or bromine atom and R and Rare defined as above, in an aqueous, aqueous-organic or organic medium,if necessary, in the presence of acid-binding agents, and by convening,if required, the basic dyestuffs thus obtained into the correspondingamine salts.

The reaction may be carried out, for example, in an alkanol of one tocarbon atoms, or in xylene, dimethyl formamide, ethylene glycol,diethylene glycol, diethylene glycol monoethyl ether, dioxane ortetrahydrofurane as organic medium. As acid-binding agents can be used,for example, alkali metal hydroxides, alkali metal carbonates, alkalimetal hydrogen carbonates or tertiary organic bases, such as pyridine,picoline or dimethyl fonnamide. The reaction is carried out attemperatures between about and about 150 C., preferably, between about80 and about 120 C. The optimal temperature for each individual case isto be adjusted according to the reaction components and the reactionmedium used. The reaction can also be carried out above or below theabove temperature range; in case of operating at lower temperatures,

or mixtures of such dyestuffs are obtained.

The molar ratio of the two reaction components is according to thedesired final product between H and 1:2, but if both primary aminogroups of the diarnine used are to be reacted, and a molar ratio of atleast l:2 is necessary, it is possible to use the compound of theabove-mentioned general. formula (3) also in an excess, for example, ina trimolar to pentamolar excess. The new dyestuffs are obtained, partly,as free bases, partly, in the form of the hydrochlorides. But they canalso be converted into the corresponding dyestuff salts, for example,into the acetates, bisulfates, sulfates, phosphates or zinc chloridedouble salts by addition of inorganic or organic acids or of suitablesalts.

The basic dyestufi's obtained according to the present invention arewater-soluble, the degree of the water-solubility, howous medium. Thedyeings and prints thus obtained possess a good fastness to light andwet processing.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto. The parts being by weight unlessotherwise stated:

EXAMPLE 1 Sixty-five and one-half parts of dipropylene triamine areadded dropwise while stirring at C. to a solution of 157.5 parts ofo-chloronitrobenzene in 50 parts of n-butanol. The mixture is heated toto l35 C. and this temperature is maintained for about l hour. Then, 42parts of sodium bicarbonate are added and stirring is continued for afurther 10 hours at this temperature. After addition of about 250 partsof ethanol the solution is cooled, and the crystal mass is filtered withsuction and washed with ethanol. The dry dyestufi' is obtained as ayellow powder in a good yield its degree of purity can still beincreased by recrystallization in glacial acetic acid.

It mainly consists of the hydrochloric salt of the double-sidedcondensation product which produces reddish-yellow dyeings of goodfastness to light on polyacrylonitrile fibers in an acid, aqueous bath.

By treating the dyestuff hydrochloride obtained in this way with adilute aqueous sodium hydroxide solution the free basic dyestuff isobtained.

EXAMPLE 2 Fifty-one and one-half parts of diethylenetriamine are addeddropwise while stirring at 80 C. to a solution of 157.5 parts ofo-chloronitrobenzene in 50 parts of n-butanol. The solution is heated tol30 to C. and the temperature is maintained for about I hour. Then 42parts of sodium bicarbonate are added and stirring is continued for afurther 10 hours at this temperature. After addition of about 250 partsof ethanol the solution is cooled and the formed double-sidedcondensation product is filtered with suction and washed with ethanol.The dry dyestufi is obtained in the form of the hydrochloride as ayellow crystal powder which produces reddish-yellow dyeings onpolyacrylonitrile fibers in acid, aqueous bath.

By treating the dyestuff hydrochloride obtained in this way with adilute aqueous sodium hydroxide solution the free basic dyestuff isobtained.

EXAMPLE 3 Sixty-five and one-half parts of dipropylenetriamine are addeddropwise while stirring at 80 C. to a suspension of 157 parts ofo-chloronitrobenzene in 60 parts of water and the mixture is stirred for1 hour at 100 C. Then, the whole is diluted with 250 parts of methanoland the hot solution is filtered. The filtrate is acidified with dilutehydrochloric acid and stirred in the cold whereby the dyestuff(double-sided condensation product) crystallizes as hydrochloric salt.It is isolated by filtration with suction, washing and drying in theform of a yellow crystal powder. The dyestuff produces reddish-yellowdyeings of a good fastness to light on polyacrylonitrile fibers in anacid, aqueous bath. By treating the dyestuff hydrochloride obtained inthis way with a dilute aqueous sodium hydroxide solution the free basicdyestuff is obtained.

EXAMPLE 4 Sixty-five parts of o-chloronitrobenzene are heated to 80 C.in about 25 parts of n-butanol while stirring.

Then 30 parts of triethylenetetramine are added dropwise and stirring iscontinued for about 1 hour. Then, 17 parts of sodium bicarbonate areadded and the temperature of the mixture is maintained for l 1 hours at125 C. After addition of about 250 parts of methanol and 50 parts ofdilute hydrochloric acid the whole is cooled while stirring. Thedouble-sided condensation product formed as a crystal mass is filteredwith suction and washed with methanol. After drying, the dyestuff isobtained as hydrochloride in the form of yellow crystals.

By treating the so obtained dyestuff hydrochloride with a dilute aqueouspotassium hydroxide solution the free basic dyestuff is obtained.

EXAMPLE In 500 parts by volume of dimethyl formamide 180 parts ofdipropylenetriamine and 330 parts of o-nitrochlorobenzene are heated to130 C. while stirring and this temperature is maintained for l2 hours.Then, the whole is cooled while stirring the double-sided condensationproduct which has precipitated in form of a crystal mass is filteredwith suction and washed with ethanol. After drying, the dyestufi' isobtained as a free base in the form of a yellow crystal powder whosedegree of purity can still be increased by recrystallization in glacialacetic acid, while, at the same time, the acetate is formed. Thedyestuff produces reddish-yellow dyeings of a good fastness to light onpolyacrylonitrile fibers in an acid, aqueous bath.

Other dyestuffs which can be produced according to the foregoingexamples in the form of the double-sided condensation products arementioned in the following table:

formed crystal mass is isolated by filtration of suction and dissolvedin a small amount of water while the sparingly soluble 2:1 condensationproduct is not dissolved. After cooling, 60

wherein R, and R each is hydrogen or chlorine, m is an integer 2 or 3, nis an integer l, 2, 3 or 4, and R is hydrogen or the group wherein R andR are defined as above, or the salt of an inorganic or organic acidthereof.

2. A dyestufi of the formula -No om or the salt of an inorganic ororganic acid thereof.

3. A dyestuff of the formula or the salt of an inorganic or organic acidthereof.

4. A dyestuff of the formula o-Nltrochlorobenzene Reaction Polyamlnecomponent component medium (1) H2N[(CH2)2NH];--(Cfizh -NH:v C1n-Butnnol.

(2) H2N-l(cH2):--NH] (CH2)2NH2 C1 D0.

(3) HzN-(CHzh-NH-(CHzh-Nfiz c1 D0.

C 1- N O 2 EXAMPLE 6 I N 0 2 N- A solution of 15 8 parts ofo-chloronitrobenzene in 130 parts of methanol is slowly added whilestirring and under reflux to a solution of 130 parts of dipropylenetriamine in 50 parts of methanol. The addition being terminated, thesolution is stirred under reflux for 5 hours.- After addition of 2 molsof concentrated hydrochloric acid, the whole is cooled. The

NIICII1 CHZ Nil-CIIg-Cllg- .\'ll (ill; (JIM-Nil or the salt of aninorganic or organic acid thereof.

5. A dyestuff of the formula 5 or the salt of an inorganic or organicacid thereof. or the salt of an inorganic or organic acid thereof.

6. A dyestuff of the formula =0:

2. A dyestuff of the formula
 3. A dyestuff of the formula
 4. A dyestuffof the formula
 5. A dyestuff of The formula
 6. A dyestuff of the formula